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What Happens Without Nickel? Cyclization Reactions of Ethylene with Ethanedithial and Related Molecules
Author(s) -
Shibl Mohamed F.,
Moncho Salvador,
Brothers Edward N.
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25142
Subject(s) - isomerization , benchmark (surveying) , olefin fiber , ethylene , nickel , chemistry , density functional theory , computational chemistry , molecule , basis set , decomposition , organic chemistry , catalysis , geodesy , geography
We present a computational study of the mechanism of the formation of 6‐member heterocycles through the binding of ethylene to oxaldehyde, ethanedithial, and 2‐thioxoacetaldehyde. This process is related to the olefin separation technology by metal dithiolenes and dioxolenes, being the formation of those heterocycles the main decomposition route. We also present a benchmark of 26 density functionals (spanning hybrid, double‐hybrid, range‐separated, semilocal, and local functionals) related to CCSD(T)/CBS reference values. Both the cyclization reaction and the isomerization of the cyclic product are included in the benchmark. The best functional among those tested for these reactions is ω B97XD, and the effect of the basis set is also investigated for it. © 2017 Wiley Periodicals, Inc.